Myopia-preventing eye-protecting ink composition and preparation method thereof

Abstract

The invention relates to the technical field of ink compositions, in particular to a myopia-preventing and eye-protecting ink composition and a preparation method thereof. The myopia-preventing and eye-protecting ink composition is prepared from the following raw material components in parts by weight: 2 to 3 parts of a modified nano material, 1.5 to 2.5 parts of essential oil sustained-release microcapsules, 1.8 to 2.7 parts of nano zinc oxide, 5 to 8 parts of octadecyl trimethoxy silane, 40 to 50 parts of a polymeric monomer, 30 to 40 parts of pigment, 2 to 3 parts of a dispersing agent, 0.5 to 1 part of a defoaming agent and 30 to 40 parts of deionized water.

Description

Technical Field

[0001] The present invention relates to the technical field of ink compositions, and in particular to an anti-myopia eye protection ink composition and a preparation method thereof. Background Art

[0002] In the prior art, some inks reflect light strongly after printing, which is prone to glare. Staring for a long time will cause eye fatigue and dryness, thereby increasing the risk of myopia. In addition, the ink components of the prior art may contain harmful chemicals. For example, the patent with application number 201911376202.5 discloses a printing ink that effectively absorbs high-energy harmful blue light to prevent myopia and a preparation and spraying method, which uses raw materials such as lead sulfate, lead chromate, and lead oxide. Therefore, the development of an ink composition and its preparation method that can meet the printing quality requirements and have anti-myopia eye protection functions has become a technical problem that needs to be solved urgently. Summary of the invention

[0003] In view of the deficiencies in the prior art, the present invention provides an anti-myopia eye protection ink composition and a preparation method thereof.

[0004] The present invention is achieved through the following technical solutions: An anti-myopia eye protection ink composition comprises the following raw materials in parts by weight: 2-3 parts of modified nanomaterials, 1.5-2.5 parts of essential oil sustained-release microcapsules, 1.8-2.7 parts of nano zinc oxide, 5-8 parts of octadecyltrimethoxysilane, 40-50 parts of polymerized monomers, 30-40 parts of pigments, 2-3 parts of dispersants, 0.5-1 parts of defoaming agents, and 30-40 parts of deionized water.

[0005] Furthermore, the polymerizable monomer is composed of the following components in parts by weight: 5-7 parts of acrylic acid, 15-20 parts of methyl methacrylate, 8-12 parts of ethyl acrylate, 6-8 parts of butyl acrylate, and 3-5 parts of hydroxypropyl methacrylate.

[0006] Furthermore, the preparation method of the modified nanomaterial comprises the following steps: A1: Prepare 0.5-1.0 mol / L aluminum chloride aqueous solution, 0.05-0.08 mol / L strontium chloride aqueous solution and 25-40 mg / mL tetrabutyl titanate ethanol solution; add the strontium chloride solution to the aluminum chloride solution at a rate of 1.5-2 mL / min under stirring at 300-400 rpm, continue stirring for 30 min, then add the tetrabutyl titanate ethanol solution at the same rate, continue stirring for 60 min, add 25-30 mg / mL PVP aqueous solution, stir for 30 min, and obtain a mixed solution; A2: Add 25 wt% ammonia water to the mixed solution obtained in step A1 at a rate of 1-2 drops per second, stir at 500-600 rpm, continue stirring for 1-2 h, transfer to a polytetrafluoroethylene-lined reactor, heat to 120-150°C at a rate of 1-3°C / min, keep warm for 12-14 h, cool to room temperature, centrifuge at 8000-10000 r / min for 10-15 min, wash the precipitate with deionized water and anhydrous ethanol alternately for 3-5 times, dry at 60-80°C, and grind to obtain an inorganic nanomaterial; A3: Add the inorganic nanomaterial obtained in step A2 to anhydrous ethanol, and ultrasonicate at 300-400 W for 15-30 min to obtain an inorganic nanomaterial dispersion. Add vinyltrimethoxysilane dropwise to a mixed solution of anhydrous ethanol and deionized water (v:v=3:1), stir at 200-300 rpm while adding dropwise, adjust the pH to 9-10, continue stirring at room temperature for 0.5-1 h, slowly add the inorganic nanomaterial dispersion, stir at 60-80°C water bath and 300-500 rpm for 4-6 h, centrifuge at 8000-10000 rpm for 10-15 min, wash the precipitate with anhydrous ethanol, and dry at 40-60°C to obtain a modified nanomaterial.

[0007] Furthermore, in step A1, the volume ratio of the aluminum chloride aqueous solution, the strontium chloride aqueous solution, the tetrabutyl titanate ethanol solution and the PVP aqueous solution is 10:2:3:1.

[0008] Furthermore, in step A2, the volume ratio of the 25 wt % ammonia water to the mixed solution is 8:1-1.5.

[0009] Furthermore, in step A3, the mass concentration of the inorganic nanomaterial in the inorganic nanomaterial dispersion in anhydrous ethanol is 8-12 mg / mL.

[0010] Furthermore, in step A3, the mass ratio of the inorganic nanomaterial to vinyltrimethoxysilane is 1:3-5.

[0011] Furthermore, in step A3, the mass concentration of the vinyltrimethoxysilane in the mixed solution of anhydrous ethanol and deionized water is 80-100 mg / mL.

[0012] Furthermore, the raw materials for preparing the essential oil sustained-release microcapsules include the following components in parts by weight: 1-2 parts of lavender essential oil, 2-3 parts of chamomile essential oil, 3-5 parts of cetyltrimethylammonium bromide, 1-2 parts of acrylic acid, 3-5 parts of methyl methacrylate, 1-2 parts of ethyl acrylate, 2-3 parts of butyl acrylate, and 0.5-0.7 parts of pentaerythritol tetraacrylate.

[0013] Furthermore, the preparation method of the essential oil sustained-release microcapsule comprises the following steps: B1: Add lavender essential oil, chamomile essential oil and cetyltrimethylammonium bromide to deionized water, emulsify and shear at 30℃ and 1500-2000 r / min for 10-15 min, and water bath at 30℃ and 800 r / min for 1-2 h; B2: After step B1 is water bathed, acrylic acid, methyl methacrylate, ethyl acrylate, and butyl acrylate are added dropwise in sequence, stirred at 300-500 r / min for 10-15 min, stirred at 60-70°C and 300-500 rpm, and pentaerythritol tetraacrylate and ammonium persulfate solution are added dropwise, and reacted for 4-6 h; B3: After the reaction in step B2 is completed, the mixture is cooled to room temperature, centrifuged at 8000 rpm for 10-15 min, the precipitate is washed with deionized water, and vacuum dried at 40-60°C to obtain essential oil sustained-release microcapsules.

[0014] Furthermore, in step B1, the mass concentration of hexadecyltrimethylammonium bromide in deionized water is 80 mg / mL.

[0015] Furthermore, in step B2, the amount of ammonium persulfate used is 10-15 wt % of the acrylic acid.

[0016] Furthermore, in step B2, the mass concentration of ammonium persulfate in the ammonium persulfate solution is 1-1.5 wt %.

[0017] Furthermore, the present invention also provides a method for preparing the anti-myopia eye protection ink, comprising the following steps: S1: Mix nano zinc oxide, octadecyltrimethoxysilane, ethanol and deionized water, heat and stir at 60-80°C for 5-6 h, centrifuge at 8000 rpm for 10-15 min, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain modified nano zinc oxide; S2: Add SDS and OP-10 to deionized water and stir to dissolve, add sodium bicarbonate, add polymerization monomers in sequence, stir at 600-700 rpm for 20-30 min, heat to 70-90°C, add ammonium persulfate, react for 30 min, add modified nanomaterials, stir at 70-90°C and 300-500 rpm for 3-5 h; S3: After the reaction in step S2 is completed, cool to room temperature, centrifuge at 3000 rpm for 5-10 min, take the supernatant, add essential oil sustained-release microcapsules, modified nano zinc oxide, pigment, dispersant, defoaming agent and deionized water, stir at 600-800 rpm for 20-30 min, and obtain an anti-myopia eye protection ink composition.

[0018] Furthermore, in step S1, the dosage ratio of the nano zinc oxide, ethanol and deionized water is 1 g:30-40 mL:10-15 mL.

[0019] Furthermore, in step S2, the amount of SDS used is 1wt%-1.5wt% of the polymerization monomers.

[0020] Furthermore, in step S2, the mass concentration of SDS in deionized water is 0.01-0.015 g / mL.

[0021] Furthermore, in step S2, the amount of OP-10 used is 1-3 wt % of the polymerization monomer.

[0022] Furthermore, in step S2, the amount of sodium bicarbonate used is 0.1wt%-0.5wt% of the polymerization monomer.

[0023] Furthermore, in step S2, the amount of ammonium persulfate used is 1-1.5 wt % of the polymerization monomer.

[0024] Compared with the prior art, the present invention has the following beneficial effects: The invention provides an anti-myopia eye protection ink composition. Lavender essential oil and chamomile essential oil in the raw materials of essential oil sustained-release microcapsules have the characteristics of soothing nerves and relaxing eye muscles. In the process of contacting printed materials containing the ink, the essential oil sustained-release microcapsules can continuously and slowly release these natural ingredients, effectively relieving eye fatigue caused by long-term eye use, and reducing the risk of myopia caused by fatigue accumulation; the modified nano material and nano zinc oxide work synergistically to absorb ultraviolet light, have the ability to adjust light, can optimize the optical properties of the printed surface, make the light reflection softer and more uniform, avoid the stimulation of strong light to the eyes, create a comfortable visual environment, and help prevent the occurrence and development of myopia; the invention adopts acrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, and hydroxypropyl methacrylate as polymerization monomers to form a polymer, which gives the ink good flexibility and strength, can withstand a certain degree of friction, enhances the adsorption of the ink, and improves the quality of the ink. The present invention uses lavender essential oil and chamomile essential oil as capsule core, acrylic acid and acrylate cross-linked copolymer as wall material, and the reaction monomers are acrylic acid, methyl methacrylate, ethyl acrylate and butyl acrylate to make microcapsules with sustained release function, solve the problem that essential oil is easy to volatilize and difficult to preserve, realize its slow release during use, prolong the efficacy time, and have high interfacial compatibility with polyacrylic acid resin, and can be evenly dispersed. The present invention uses aluminum chloride, strontium chloride, and tetrabutyl titanate to prepare nanomaterials, and through surface modification of vinyl trimethoxysilane, double bonds are grafted on the surface of the nanomaterials to make it participate in the polymerization of polyacrylic acid resin, and the nanomaterials are combined with the polypropylene resin molecular chain to improve dispersibility and effectively prevent agglomeration. After nano zinc oxide is modified by octadecyl trimethoxysilane, the hydrophobicity is significantly improved, and the binding force with other organic components is enhanced, the interfacial compatibility is improved, and it is evenly dispersed in the system, which can improve the water resistance of the ink composition, and the nanomaterial can be filled in the polymer network structure to enhance the density and improve the stability. The pigment can be evenly dispersed in the ink under the synergistic effect of the modified nanomaterial, dispersant and polymerized monomer, and the ink can effectively adhere to the surface of the printed substrate, with bright colors and uniformity. The overall formula of the ink composition of the present invention will not release volatile substances harmful to the human body and the environment during use, has low irritation, and can be applied to printed materials such as student exercise books and learning materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only for the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0026] Figure 1is the reflectivity of the ink composition described in Examples 1-3 and Comparative Examples 2-3 of the present invention; Figure 2 The eye protection effect of the ink composition described in Examples 1-3 and Comparative Examples 1-3 of the present invention; Figure 3 The friction resistance of the ink composition described in Examples 1-3 and Comparative Examples 1-3 of the present invention; Figure 4 The water resistance of the ink composition described in Examples 1-3 and Comparative Examples 1-3 of the present invention; Figure 5 It is the adhesion degree of the ink composition described in Examples 1-3 of the present invention and Comparative Examples 1-3. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments. It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention are purchased through commercial channels.

[0028] Example 1: An anti-myopia eye protection ink composition comprises the following raw materials in parts by weight: 3 parts of modified nanomaterials, 2.5 parts of essential oil sustained-release microcapsules, 2.7 parts of nano zinc oxide, 8 parts of octadecyltrimethoxysilane, 50 parts of polymerization monomers, 40 parts of pigments, 3 parts of dispersants, 1 part of defoaming agents, and 40 parts of deionized water.

[0029] The polymerizable monomers are composed of the following components in parts by weight: 7 parts of acrylic acid, 20 parts of methyl methacrylate, 12 parts of ethyl acrylate, 8 parts of butyl acrylate, and 5 parts of hydroxypropyl methacrylate.

[0030] The preparation method of the modified nanomaterial comprises the following steps: A1: Prepare 1.0 mol / L aluminum chloride aqueous solution, 0.08 mol / L strontium chloride aqueous solution and 40 mg / mL tetrabutyl titanate ethanol solution; add the strontium chloride solution to the aluminum chloride solution at a rate of 2 mL / min under stirring at 400 rpm, continue stirring for 30 min, then add the tetrabutyl titanate ethanol solution at the same rate, continue stirring for 60 min, add 30 mg / mL PVP aqueous solution, the volume ratio of aluminum chloride aqueous solution, strontium chloride aqueous solution, tetrabutyl titanate ethanol solution and PVP aqueous solution is 10:2:3:1, stir for 30 min to obtain a mixed solution; A2: Add 25 wt% ammonia water to the mixed solution obtained in step A1 at a rate of 2 drops per second, the volume ratio of 25 wt% ammonia water to the mixed solution is 8:1.5, and stir at 600 rpm. Continue stirring for 2 h, transfer to a polytetrafluoroethylene-lined reactor, heat to 150°C at a rate of 3°C / min, keep warm for 14 h, cool to room temperature, centrifuge at 10000 r / min for 15 min, wash the precipitate alternately with deionized water and anhydrous ethanol for 5 times, dry at 80°C, and grind to obtain an inorganic nanomaterial; A3: The inorganic nanomaterial obtained in step A2 was added to anhydrous ethanol, and ultrasonicated at 400 W for 30 min to obtain a 12 mg / mL inorganic nanomaterial dispersion. Vinyltrimethoxysilane was added dropwise at a ratio of 100 mg / mL to a mixed solution of anhydrous ethanol and deionized water (v:v=3:1), and stirred at 300 rpm while adding dropwise. The pH was adjusted to 10, and stirring was continued at room temperature for 1 h. The inorganic nanomaterial dispersion was slowly added, and the mass ratio of the inorganic nanomaterial to vinyltrimethoxysilane was 1:5. The mixture was stirred at 80°C water bath and 500 rpm for 6 h. The mixture was centrifuged at 10,000 rpm for 15 min. The precipitate was washed with anhydrous ethanol and dried at 60°C to obtain a modified nanomaterial.

[0031] The raw materials for preparing essential oil sustained-release microcapsules include the following components in parts by weight: 2 parts of lavender essential oil, 3 parts of chamomile essential oil, 5 parts of cetyltrimethylammonium bromide, 2 parts of acrylic acid, 5 parts of methyl methacrylate, 2 parts of ethyl acrylate, 3 parts of butyl acrylate, and 0.7 parts of pentaerythritol tetraacrylate.

[0032] The preparation method of essential oil sustained-release microcapsules comprises the following steps: B1: Add 2 g lavender essential oil, 3 g chamomile essential oil and 5 g cetyltrimethylammonium bromide to 62.5 mL deionized water, emulsify and shear at 30°C and 2000 r / min for 15 min, and water bath at 30°C and 800 r / min for 2 h; B2: After step B1 is placed in a water bath, 2 g of acrylic acid, 5 g of methyl methacrylate, 2 g of ethyl acrylate, and 3 g of butyl acrylate are added dropwise in sequence, stirred at 500 r / min for 15 min, stirred at 70°C and 500 rpm, 0.7 g of pentaerythritol tetraacrylate and a 1.5 wt% solution prepared with 0.3 g of ammonium persulfate are added dropwise, and the reaction is continued for 6 h; B3: After the reaction in step B2 is completed, the mixture is cooled to room temperature, centrifuged at 8000 rpm for 15 min, the precipitate is washed with deionized water, and vacuum dried at 60°C to obtain essential oil sustained-release microcapsules.

[0033] This embodiment also provides a method for preparing the anti-myopia eye protection ink, comprising the following steps: S1: Mix 2.7 g of nano zinc oxide, 8 g of octadecyltrimethoxysilane, 108 mL of ethanol and 40.5 mL of deionized water, heat and stir at 80 °C for 6 h, centrifuge at 8000 rpm for 15 min, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain modified nano zinc oxide; S2: Add 0.75 g SDS and 1.5 g OP-10 to 50 mL deionized water and stir to dissolve, add 0.25 g sodium bicarbonate, add 50 g polymerization monomers in turn, stir at 700 rpm for 30 min, heat to 90 ° C, add 0.75 g ammonium persulfate, react for 30 min, add 3 g modified nanomaterials, stir at 90 ° C, 500 rpm for 5 h; S3: After the reaction in step S2 is completed, cool to room temperature, centrifuge at 3000 rpm for 10 min, take the supernatant, add 2.5 g of essential oil sustained-release microcapsules, modified nano zinc oxide, 40 g of pigment, 3 g of dispersant, 1 g of defoaming agent and 40 g of deionized water, stir at 800 rpm for 30 min to obtain an anti-myopia eye protection ink composition.

[0034] Example 2: An anti-myopia eye protection ink composition comprises the following raw materials in parts by weight: 2 parts of modified nanomaterials, 1.5 parts of essential oil sustained-release microcapsules, 1.8 parts of nano zinc oxide, 5 parts of octadecyltrimethoxysilane, 40 parts of polymerization monomers, 30 parts of pigments, 2 parts of dispersants, 0.5 parts of defoaming agents, and 30 parts of deionized water.

[0035] The polymerizable monomers are composed of the following components in parts by weight: 5 parts of acrylic acid, 15 parts of methyl methacrylate, 8 parts of ethyl acrylate, 6 parts of butyl acrylate, and 3 parts of hydroxypropyl methacrylate.

[0036] The preparation method of the modified nanomaterial comprises the following steps: A1: Prepare 0.5 mol / L aluminum chloride aqueous solution, 0.05 mol / L strontium chloride aqueous solution and 25 mg / mL tetrabutyl titanate ethanol solution; add the strontium chloride solution to the aluminum chloride solution at a rate of 1.5 mL / min under stirring at 300 rpm, continue stirring for 30 min, then add the tetrabutyl titanate ethanol solution at the same rate, continue stirring for 60 min, add 25 mg / mL PVP aqueous solution, the volume ratio of aluminum chloride aqueous solution, strontium chloride aqueous solution, tetrabutyl titanate ethanol solution and PVP aqueous solution is 10:2:3:1, stir for 30 min to obtain a mixed solution; A2: Add 25 wt% ammonia water to the mixed solution obtained in step A1 at a rate of 1 drop per second, the volume ratio of 25 wt% ammonia water to the mixed solution is 8:1, and stir at 500 rpm. Continue stirring for 1 h, transfer to a polytetrafluoroethylene-lined reactor, heat to 120°C at a rate of 1°C / min, keep warm for 12 h, cool to room temperature, centrifuge at 8000 r / min for 10 min, wash the precipitate alternately with deionized water and anhydrous ethanol for 3 times, dry at 60°C, and grind to obtain an inorganic nanomaterial; A3: The inorganic nanomaterial obtained in step A2 was added to anhydrous ethanol, and ultrasonicated at 300 W for 15 min to obtain an 8 mg / mL inorganic nanomaterial dispersion. Vinyltrimethoxysilane was added dropwise at a ratio of 80 mg / mL to a mixed solution of anhydrous ethanol and deionized water (v:v=3:1), and stirred at 200 rpm while adding dropwise. The pH was adjusted to 9, and stirring was continued at room temperature for 0.5 h. The inorganic nanomaterial dispersion was slowly added, and the mass ratio of the inorganic nanomaterial to vinyltrimethoxysilane was 1:3. The mixture was stirred at 300 rpm for 4 h in a 60°C water bath, and centrifuged at 8000 rpm for 10 min. The precipitate was washed with anhydrous ethanol and dried at 40°C to obtain a modified nanomaterial.

[0037] The raw materials for preparing essential oil sustained-release microcapsules include the following components in parts by weight: 1 part of lavender essential oil, 2 parts of chamomile essential oil, 3 parts of cetyltrimethylammonium bromide, 1 part of acrylic acid, 3 parts of methyl methacrylate, 1 part of ethyl acrylate, 2 parts of butyl acrylate, and 0.5 parts of pentaerythritol tetraacrylate.

[0038] The preparation method of essential oil sustained-release microcapsules comprises the following steps: B1: Add 1 g lavender essential oil, 2 g chamomile essential oil and 3 g cetyltrimethylammonium bromide to 37.5 mL deionized water, emulsify and shear at 30°C and 1500 r / min for 10 min, and water bath at 30°C and 800 r / min for 1 h; B2: After step B1 in a water bath, 1 g of acrylic acid, 3 g of methyl methacrylate, 1 g of ethyl acrylate, and 2 g of butyl acrylate were added dropwise in sequence, stirred at 300 r / min for 10 min, stirred at 60°C and 300 rpm, and a 1 wt% solution of 0.5 g of pentaerythritol tetraacrylate and 0.1 g of ammonium persulfate was added dropwise, and the reaction was continued for 4 h; B3: After the reaction in step B2 is completed, the mixture is cooled to room temperature and centrifuged at 8000 rpm for 10 min. The precipitate is washed with deionized water and dried under vacuum at 40°C to obtain essential oil sustained-release microcapsules.

[0039] This embodiment also provides a method for preparing the anti-myopia eye protection ink, comprising the following steps: S1: Mix 1.8 g of nano zinc oxide, 5 g of octadecyltrimethoxysilane, 54 mL of ethanol and 18 mL of deionized water, heat and stir at 60°C for 5 h, centrifuge at 8000 rpm for 10 min, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain modified nano zinc oxide; S2: Add 0.4 g SDS and 0.4 g OP-10 to 40 mL deionized water and stir to dissolve, add 0.04 g sodium bicarbonate, add 40 g polymerization monomers in turn, stir at 600 rpm for 20 min, heat to 70°C, add 0.4 g ammonium persulfate, react for 30 min, add 2 g modified nanomaterials, stir at 70°C and 300 rpm for 3 h; S3: After the reaction in step S2 is completed, cool to room temperature, centrifuge at 3000 rpm for 5 min, take the supernatant, add 1.5 g of essential oil sustained-release microcapsules, modified nano zinc oxide, 30 g of pigment, 2 g of dispersant, 0.5 g of defoaming agent and 30 g of deionized water, stir at 600 rpm for 20 min to obtain an anti-myopia eye protection ink composition.

[0040] Example 3: An anti-myopia eye protection ink composition comprises the following raw materials in parts by weight: 2.5 parts of modified nanomaterials, 2 parts of essential oil sustained-release microcapsules, 2 parts of nano zinc oxide, 6 parts of octadecyltrimethoxysilane, 45 parts of polymerization monomers, 35 parts of pigments, 2.5 parts of dispersants, 0.8 parts of defoaming agents, and 35 parts of deionized water.

[0041] The polymerizable monomers are composed of the following components in parts by weight: 6 parts of acrylic acid, 18 parts of methyl methacrylate, 10 parts of ethyl acrylate, 7 parts of butyl acrylate, and 4 parts of hydroxypropyl methacrylate.

[0042] The preparation method of the modified nanomaterial comprises the following steps: A1: Prepare 0.8 mol / L aluminum chloride aqueous solution, 0.06 mol / L strontium chloride aqueous solution and 35 mg / mL tetrabutyl titanate ethanol solution; add the strontium chloride solution to the aluminum chloride solution at a rate of 1.8 mL / min under stirring at 350 rpm, continue stirring for 30 min, then add the tetrabutyl titanate ethanol solution at the same rate, continue stirring for 60 min, add 28 mg / mL PVP aqueous solution, the volume ratio of aluminum chloride aqueous solution, strontium chloride aqueous solution, tetrabutyl titanate ethanol solution and PVP aqueous solution is 10:2:3:1, stir for 30 min to obtain a mixed solution; A2: Add 25 wt% ammonia water to the mixed solution obtained in step A1 at a rate of 2 drops per second, the volume ratio of 25 wt% ammonia water to the mixed solution is 8:1.2, and stir at 550 rpm. Continue stirring for 1.5 h, transfer to a polytetrafluoroethylene-lined reactor, heat to 130°C at a rate of 2°C / min, keep warm for 13 h, cool to room temperature, centrifuge at 9000 r / min for 12 min, wash the precipitate alternately with deionized water and anhydrous ethanol for 4 times, dry at 70°C, and grind to obtain an inorganic nanomaterial; A3: The inorganic nanomaterial obtained in step A2 was added to anhydrous ethanol, and ultrasonicated at 350 W for 20 min to obtain a 10 mg / mL inorganic nanomaterial dispersion. Vinyltrimethoxysilane was added dropwise at a ratio of 90 mg / mL to a mixed solution of anhydrous ethanol and deionized water (v:v=3:1), and stirred at 250 rpm while adding dropwise. The pH was adjusted to 9.5, and stirring was continued at room temperature for 0.7 h. The inorganic nanomaterial dispersion was slowly added, and the mass ratio of the inorganic nanomaterial to vinyltrimethoxysilane was 1:4. The mixture was stirred at 400 rpm in a 70°C water bath for 5 h, and centrifuged at 9000 rpm for 12 min. The precipitate was washed with anhydrous ethanol and dried at 50°C to obtain a modified nanomaterial.

[0043] The raw materials for preparing essential oil sustained-release microcapsules include the following components in parts by weight: 1.5 parts of lavender essential oil, 2.5 parts of chamomile essential oil, 4 parts of cetyltrimethylammonium bromide, 1.5 parts of acrylic acid, 4 parts of methyl methacrylate, 1.5 parts of ethyl acrylate, 2.5 parts of butyl acrylate, and 0.6 parts of pentaerythritol tetraacrylate.

[0044] The preparation method of essential oil sustained-release microcapsules comprises the following steps: B1: Add 1.5 g lavender essential oil, 2.5 g chamomile essential oil and 4 g cetyltrimethylammonium bromide to 50 mL deionized water, emulsify and shear at 30°C and 1800 r / min for 12 min, and water bath at 30°C and 800 r / min for 1.5 h; B2: After step B1 is placed in a water bath, 1.5 g of acrylic acid, 4 g of methyl methacrylate, 1.5 g of ethyl acrylate, and 2.5 g of butyl acrylate are added dropwise in sequence, stirred at 400 r / min for 12 min, stirred at 65°C and 400 rpm, and a 1.2 wt% solution of 0.6 g of pentaerythritol tetraacrylate and 0.18 g of ammonium persulfate is added dropwise, and the reaction is continued for 5 h; B3: After the reaction in step B2 is completed, the mixture is cooled to room temperature and centrifuged at 8000 rpm for 12 min. The precipitate is washed with deionized water and dried under vacuum at 50°C to obtain essential oil sustained-release microcapsules.

[0045] This embodiment also provides a method for preparing the anti-myopia eye protection ink, comprising the following steps: S1: Mix 2 g of nano zinc oxide, 6 g of octadecyltrimethoxysilane, 70 mL of ethanol and 24 mL of deionized water, heat and stir at 70 °C for 5.5 h, centrifuge at 8000 rpm for 12 min, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain modified nano zinc oxide; S2: Add 0.54 g SDS and 0.9 g OP-10 to 45 mL deionized water and stir to dissolve, add 0.15 g sodium bicarbonate, add 45 g polymerization monomers in turn, stir at 650 rpm for 25 min, heat to 80 ° C, add 0.54 g ammonium persulfate, react for 30 min, add 2.5 g modified nanomaterials, stir at 80 ° C, 400 rpm for 4 h; S3: After the reaction in step S2 is completed, cool to room temperature, centrifuge at 3000 rpm for 8 min, take the supernatant, add 2 g of essential oil sustained-release microcapsules, modified nano zinc oxide, 35 g of pigment, 2.5 g of dispersant, 0.8 g of defoaming agent and 35 g of deionized water, stir at 700 rpm for 25 min to obtain an anti-myopia eye protection ink composition.

[0046] The only difference between Comparative Example 1 and Example 1 is that no essential oil sustained-release microcapsules are added.

[0047] The only difference between Comparative Example 2 and Example 1 is that no modified nanomaterial is added.

[0048] The only difference between Comparative Example 3 and Example 1 is that no modified nano zinc oxide is added.

[0049] Experimental Example 1: The ink composition sample prepared in Example 1 was taken to detect the amount of harmful elements contained therein. The results are shown in Table 1.

[0050] Table 1:

[0051] The results in Table 1 show that the ink composition of the present invention does not contain elements with high biological toxicity, passes the quality inspection, is non-toxic and harmless, and has high safety.

[0052] Experimental Example 2: The inks prepared in Examples 1-3 and Comparative Examples 2-3 were printed on a substrate, and the UV-visible diffuse reflectance data of the inks prepared in Examples 1-3 and Comparative Examples 2-3 within a wavelength range of 380-500 nm were measured by a UV-visible diffuse reflectance spectrophotometer. The lower the reflectance, the less likely it is that light that is harmful to the human eye will irritate the human eye, and the better the eye protection performance of the ink. The results are as follows: Figure 1 shown.

[0053] Figure 1 The results show that the reflectivity of Examples 1-3 is significantly lower than that of Comparative Examples 2-3. Comparative Examples 2 and 3 did not add modified nanomaterials and nano zinc oxide, respectively. The prepared ink compositions lacked some nanomaterials, and the reflectivity to harmful light increased, reducing the eye protection effect.

[0054] Experimental Example 3: Recruit 100 adolescent volunteers aged 12-18 years old. Adolescents in this age group have great eye needs and a high incidence of myopia. Volunteers need to have normal vision or mild myopia (myopia degree ≤ -3.00D), and have not used other anti-myopia products in the past 3 months. The volunteers were randomly divided into 5 groups, 20 in each group, corresponding to Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively. A control group of ordinary commercially available ink was also set up. Each volunteer used a workbook printed with the corresponding ink for writing and reading every day, with a usage time of no less than 4 hours for 8 weeks. The subjective feelings of the volunteers were collected through questionnaires every two weeks, including eye fatigue, dryness, soreness, etc., 1 point means no obvious feeling, 5 points means a very strong feeling, to evaluate the effects of different inks on eye comfort. Before and after the experiment, the naked eye vision and refractive power of the volunteers were measured using a standard logarithmic visual acuity chart and a computer ophthalmometer, respectively, and the changes in vision of volunteers in different groups were compared to determine the protective and improvement effects of the ink on vision. The results are as follows: Figure 2 shown.

[0055] Figure 2 The results showed that after 8 weeks of use, the subjective perception scores of eye discomfort in Example 1 and Comparative Examples 1-3 were significantly reduced, and the eye protection effect was better than that of the control group, among which Example 1 had the best effect. Comparative Example 1 did not add essential oil sustained-release microcapsules, and would not sustainably release essential oils, and the effect of relieving visual fatigue was reduced. Comparative Examples 2 and 3 did not add modified nanomaterials and nano zinc oxide, and the absorption rate of harmful light was reduced, and the eye protection effect was reduced.

[0056] Experimental Example 4: Test the friction resistance of ink with reference to "GB / T 7706-2008 Letterpress Decorative Printings". Cut the cardboard and A4 paper into 6cm×30cm and 5cm×30cm strips respectively for use. Take an appropriate amount of ink and drop it in the gap between the rubber wheel of the color spreading wheel and the anilox roller, spread the ink evenly on the cardboard, and put the strips into the oven for drying for 1 min. Then fix the strips on the lower friction table of the ink printing decolorizer, wrap the dust-free A4 white paper on the upper friction table, and fix it on the transmission arm, and place a 2 kg weight on it, and perform 50 reciprocating friction tests at a speed of 85 r / min. Measure the color density before and after friction, and calculate the wear resistance. Wear resistance (%) = (color density before friction / color density after friction) × 100%. The results are as follows Figure 3 shown.

[0057] Figure 3 The results show that the friction properties of Examples 1-3 are higher than those of Comparative Examples 1-3, and the friction resistance is better than that of Comparative Examples 1-3, with good friction resistance. Comparative Example 1 does not add essential oil sustained-release microcapsules, and the friction resistance decreases to a certain extent. Comparative Example 2 does not add modified nanomaterials, and the friction resistance decreases. Comparative Example 3 does not add modified nano zinc oxide, the ink density decreases, and the friction resistance decreases.

[0058] Experimental Example 5: The ink compositions prepared in Examples 1-3 and Comparative Examples 1-3 were poured onto a polytetrafluoroethylene plate, evenly spread and placed in an oven at 30°C to dry, to obtain corresponding ink composition films. Water was dripped on the film surface to observe the contact angle. The results were as follows: Figure 4 shown.

[0059] Figure 4 The results show that the contact angles of Examples 1-3 are greater than those of Comparative Examples 1-3, indicating that the anti-myopia eye protection ink of the present invention has good water resistance. Comparative Example 1 does not add essential oil sustained-release microcapsules, which affects the density of the ink composition and reduces water resistance. Comparative Example 2 does not add modified nanomaterials, and the water resistance decreases. Comparative Example 4 does not add modified nano zinc oxide and does not introduce hydrophobic long-chain silane coupling agents, which reduces hydrophobicity and density, increases the difficulty for water molecules to enter the interior, and reduces water resistance.

[0060] Experimental Example 6: Using PET film as the printing substrate and 3M tape, the adsorption force of the ink compositions of Examples 1-3 and Comparative Examples 1-3 was tested by the hundred-word grid test method, and the adhesion fastness was calculated. Adhesion fastness (%) = [A1 / (A1+A2)] × 100%, where A1 represents the number of grids of the ink layer; A2 represents the number of grids of the ink layer that was peeled off. The results are as follows: Figure 5 shown.

[0061] Figure 5 The results show that the ink adhesion of Example 1-3 is better than that of Comparative Example 1-3, indicating that the anti-myopia eye protection ink composition of the present invention has high adhesion and excellent performance. In addition, the ink compositions obtained in Examples 1-3 and Comparative Examples 1-3 of the present application were tested for storage stability for 9 months at 25°C and sealed conditions. The test results show that after 9 months, no agglomeration or flocculation occurred in each group of inks. This shows that the ink composition obtained in the present application has good storage stability, and the ink composition prepared by the present invention has excellent performance in all aspects.

[0062] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

Claims

1. An anti-myopia eye protection ink composition, characterized in that: The raw materials include: modified nanomaterials, essential oil sustained-release microcapsules, nano zinc oxide, octadecyltrimethoxysilane, polymerization monomers, pigments, dispersants, defoamers, and deionized water; The preparation method of the modified nanomaterial comprises the following steps: A1: Prepare an aluminum chloride aqueous solution, a strontium chloride aqueous solution and a tetrabutyl titanate ethanol solution; add the strontium chloride solution to the aluminum chloride solution, then dropwise add the tetrabutyl titanate ethanol solution, stir, and add the PVP aqueous solution to obtain a mixed solution; A2: adding ammonia water dropwise to the mixed solution obtained in step A1, stirring, heating to react, cooling, centrifuging, washing the precipitate, drying, and grinding to obtain an inorganic nanomaterial; A3: adding the inorganic nanomaterial obtained in step A2 to anhydrous ethanol, ultrasonicating to obtain an inorganic nanomaterial dispersion, dropping vinyltrimethoxysilane into the anhydrous ethanol and deionized water mixed solution, adjusting the pH, adding the inorganic nanomaterial dispersion, water bathing, stirring, centrifuging, washing the precipitate, and drying to obtain a modified nanomaterial; The preparation method of the essential oil sustained-release microcapsule comprises the following steps: B1: Add 1-2 parts of lavender essential oil, 2-3 parts of chamomile essential oil and 3-5 parts of cetyltrimethylammonium bromide to deionized water, emulsify and shear, and water bath; B2: After step B1 is water bathed, 1-2 parts of acrylic acid, 3-5 parts of methyl methacrylate, 1-2 parts of ethyl acrylate, and 2-3 parts of butyl acrylate are added dropwise in sequence, and stirred. Then, 0.5-0.7 parts of pentaerythritol tetraacrylate and ammonium persulfate solution are added dropwise to react; B3: After the reaction in step B2 is completed, the reaction is cooled, centrifuged, the precipitate is washed, and dried to obtain essential oil sustained-release microcapsules.

2. The anti-myopia eye protection ink composition according to claim 1, characterized in that: In step A1, the volume ratio of the aluminum chloride aqueous solution, the strontium chloride aqueous solution, the tetrabutyl titanate ethanol solution and the PVP aqueous solution is 10:2:3:1; in step A2, the volume ratio of the ammonia water to the mixed solution is 8:1-1.5; in step A3, the mass concentration of the inorganic nanomaterial in anhydrous ethanol is 8-12 mg / mL; the mass ratio of the inorganic nanomaterial to vinyltrimethoxysilane is 1:3-5; the mass concentration of vinyltrimethoxysilane in the anhydrous ethanol and deionized water mixed solution is 80-100 mg / mL.

3. The anti-myopia eye protection ink composition according to claim 4, characterized in that: In step B1, the mass concentration of hexadecyltrimethylammonium bromide in deionized water is 80 mg / mL.

4. A method for preparing the anti-myopia eye protection ink composition according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1: 1.8-2.7 parts of nano zinc oxide, ethanol and deionized water in a ratio of 1 g:30-40 mL:10-15 mL, and 5-8 parts of octadecyltrimethoxysilane are mixed, reacted, centrifuged, precipitated, washed, and dried to obtain modified nano zinc oxide; S2: Add SDS and OP-10 to deionized water to dissolve, add sodium bicarbonate, add 40-50 parts of polymerization monomers in sequence, stir, heat, add ammonium persulfate, react, add 2-3 parts of modified nanomaterials, stir and react; S3: After the reaction in step S2 is completed, cool and centrifuge, take the supernatant, add 1.5-2.5 parts of essential oil sustained-release microcapsules, modified nano zinc oxide, 30-40 parts of pigment, 2-3 parts of dispersant, 0.5-1 part of defoaming agent and 30-40 parts of deionized water, stir, and obtain an anti-myopia eye protection ink composition.

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